DE1770202B2 - Process for the production of high molecular weight polyamide-imides - Google Patents

Description

'5

Il ο

in which R ₄ denotes an aliphatic, aliphatic-aromatic or aromatic radical which is at least simply replaced by a radical —OH.

Ij

-COR ₅ R ₅ OR ₅

^! Il I

-NCNR ₅

SO ₃ -R ₅

- C—

where R _{5 is} a hydrogen atom, an alkyl. Aryl or aralkyl resl is substituted. or with cyclic dianhydrides of the general formula

45

O i

^V O-2

in which R _{4 is} an aliphatic or aromatic radical or a radical of the general form!

—NH-C

Ii ο

i! c

i!

C-NH-

Il ο

Il c

/ ■

Il ο

-CO-CH ₂ -CH ₂ -OC

represents, or with cyclic trianhydrides of the general formula

CHOIR

CHOIR

CH ₂ -OR

a remainder in row

Il c-

means, optionally in an organic solvent, at temperatures from 0 to 350 C. characterized in that the reaction is carried out in the presence of lactams all my formula

NH

[R ₇ -C IVJ

in which χ is an integer from 2 to 20 and R ₆ and R are the same or different and have the meanings given _{for R 5.}

2. The method according to claim 1, characterized in that the conversion is carried out in the present of catalysts.

3. The method according to claim 1, characterized in that the implementation in Gegenwar of glycols.

Y ^y

denotes, where X is a radical of the formulas - C - - N = N - - O

It is already known that one obtains when aliphatic ^ · or aromatic diamine with dicarboxylic acid carboxylic acid chloride z. B. with trimeilitic anhydride chloride. to the umsei / ung be brought. A disadvantage of this process is that it neutralizes the halogen Hydrogen acid acceptors must be added;

; en. whose salts then interfere in the polymer and only through difficult and cumbersome cleaning operations, which are often worsened by splitting or rearrangement reactions the mechanical properties are to be removed.

It is also known from French patent 1375 461, optionally masked polyisocyanates to react with cyclic carboxylic anhydrides at 50 to 200 ° C in a solvent (see in particular page 1, left column, last paragraph to right column, 2nd paragraph, page 2, right column. Paragraphs 1 to 4).

The polyamide-imides find z. B. as paints and insulating films Used in electronics, as there are numerous combinations from this series special thermal resistance.

The invention now relates to a process for the production of high molecular weight polyamide-imides by reacting aliphatic, aromatic or aliphatic-aromatic diisocyanates with cyclic carboxylic acid anhydrides of the general formula

or a radical of the general formula

denotes, where X is a radical of the formulas

- C

-N = N-

-O-

C-NH-

CO-CH ₂ -CH ₂ -OC

represents, or with cyclic trianhydrides in which R ₄ denotes an aliphatic, aliphatic-aromatic general formula or aromatic radical which is at least 35 simply replaced by a radical —OH.

CH ₁ -OR

Il

-COR ₅ R, OR ₅

Γ Il I "

--NCNR ₅ OR,

Il / '

- C-N

40

45 a remainder in row

i |

- Q-

CHOIR

CH ₂ -OR
O

50 means, optionally in an organic solvent, at temperatures from 0 to 350.degree. which is characterized by it. that you can implement

where R _{5 is} a hydrogen atom, an alkyl. Aryl in the presence of lactams of the general formula or aralkyl radical, is substituted, or with 55 cyclic dianhydrides of the general formula NH

[R ₇ -CR ₁ , _ _x ] 10, C --- O

C)

65

in which R _{1 is} an aliphatic or aromatic radical in which λ is an integer from 2 to 20 and R ₁ and R ^ are identical or different and have the meaning given _{for R 5.}

In this way, for example, high molecular weight polyamide-imides are obtained.

The method according to the invention makes it possible. the ones that are often difficult to clean and that are damnable Replace polyamines with the .11 most distillable polyisocyanates.

Since only carbon dioxide is produced as a low molecular weight reaction product, these are often omitted in addition to the technical effort, with chain splitting and thus a deterioration of the mechanical values associated cleaning operations. By the duration of heating and the choice of stoichiometric Ratios, the average molecular weights can be varied within wide limits.

Since no water is produced in the course of the condensation either, hydrolysis reactions are avoided. In contrast to the reaction of acid anhydrides with isocyanates, side reactions take place, e.g. B. Networks, only to a negligible extent, and predominantly high molecular weight condensation products are obtained with a low degree of branching, which are characterized by particularly good solubilities.

Suitable lactams for the process according to the invention are those having the general formula

, - "'' NH

in which R ₇ and R _{6 are} identical or different and have the meaning given for R ₅ and χ represents an integer from 2 to 20.

Examples are the lactams used according to the invention

NH-

-NH-

Il

c ^/

I! ο

[CH ₂ ],

C = O

NH

C = O

[CH ₂ ] ₅

[CH ₂ ] ,,

-NH C ₂ H ₅ -CH NH

C = O

[CH ₂ LC = O

Ph-CH

I NH

[CH ₂ ], I.

I c = o

Ph-CH) H ₃ C

H ₃ C [CH ₂ L NH

C C = O

40 HX-O-R

Ί ii

HC-O-R R = -C

H ₂ COR

Il

/ Cv / O

Il

C \

Il

C \

C- '

Il

Il

HOOC

/ VC \

45 Il O

Caprolaciam or α-aminododecanoic acid lactam is preferably used.
Examples of the door used according to the invention

cyclic carboxylic anhydrides are: O
I] 50 O
Ij O
11th -CH ₂ -COOH O
π O P. / Cs
O Il
C-CH ₂ ο _Λ Il
\\ / V ^c 0 0 O = C C = O ^v Ύ Il / \ I. Il. Il 1 1 ! I
O O CH- ό / C \ _v / \ / C \ Il
O 55 \ / 0 T ί 0 C-CH ₂ ^X C ^/ \ y / ^V C ^/ I I 11th
Il Il Il Vv O 0 0 O = C C = O 60 0 O / Cy / \ Y
0 1 ij_iL J \ °
f) \ Il Il Js ₅ ^ CO-CH ₂ - Il
O

-J \

Il

C)

Connections are used, which are like \ - / \ - /

z. B. o-dicarboxylic acids or their phenyl esters im

Convert the course of the reaction into acid anhydrides </ "" ^S V_n ^ \

permit. Trimellitic acid anhy- / C == / "\ __ X are preferably suitable

drid, pyromellitic anhydride and azo-4,4'-bis-15 O = ^ = C = N N = C phthalic anhydride.

0-

gm e Eg p,
aliphatic-aromatic diisocyanates.
Such isocyanates are, for example:

r η

= O

O = C = N- [CH ₂ ] ₆ -N = C = O

O = C = N-CH ₂ N = C = O

= C = O

CH ₃ CH ₃

I I

O = C = N-CH ₂ -C-CH ₂ -CH-CH ₂ -CH ₂ -N = C = O
CH ₃

C O

₄ o

o = c = N

—C — o [- ch _{2 —Ch 2} -o—] .— c — nh - <(h VI = C = O

I Il /,

-JO-C ₂ H ₄ -C- ^ -NH

O = C = N- [CH ₂ ] ₆ -NH-C-

O

Il Il

0-C ₃ H ,, - 0-C-NH- [CHj] ₆ -NH-C-

-0-C ₃ H ₆ -OC-NH- [CH ₂ LN = C =

The following are preferably used:

4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate and hexamethylene diisocyanate.

Instead of the isocyanates, it is also possible to use compounds which react as isocyanates under the reaction conditions, e.g. B. masked isocyanates such as the addition products of phenols. Hydrocyanic acid and CH-acidic compounds, e.g. B. of cyclohexanone. Particularly noteworthy are a the adducts of lactams, ζ. B. caprolactam. Isocyanates. Furthermore, derivatives of isocyanates can be used as starting products for the reaction according to the invention, which are
Urea and alkyl carbamic acid esters with c> see acid amhydrides to imides and with carb acids to convert to amides.

409 52i

The process according to the invention is illustrated by the following reaction scheme:

NH

O + [CH ₂ I ₅ I + O = C = N = R'-
C / ..- C = O

- R— '.

C '

N- [CH ₂ J ₅ -C -NH-R'- + CO ₂

Are at least up to functional c Isocyanates and bisfunctional acid anhydrides are used, the linkage takes place Monomers or oligomers for high molecular weight connection only via amide and imide groups. But you can also choose the high molecular weight compounds from a monofunctional and a bisfunctional or from two monofunctional components, but then at least a second one must have a condensation or addition group. For example, from 4,4-diisocyanato-diphenylmelane. Caprolactam and trimellitic anhydride polyamidimide with varied Amide-fmid ratio obtained.

Another option from lactams, monofunctional Acid anhydrides and isocyanates with a second reactive group high molecular weight Building connections consists in adding diols. For example, one obtains from dodecanoic acid lactam, trimellitic anhydride. Toluylene- (2.4) -diisocyanal and hexanediol the corresponding Poly-amide-imide-ester.

The reaction according to the invention can be carried out in solvents which do not react or only loosely with the components under the reaction conditions Addition compounds or compounds which react further, form, are carried out. Suitable solvents are (halogenated hydrocarbons, phenols, esters, ketones, ethers, substituted amides, sulfoxides and sulfones, for example xylene, o-dichlorobenzene. Phenol. Cresol. Acetophenone. Glycol monomethyl ether acetate. N-methyl-pyrrolidone. Dimethylformamide. Dimethyl sulfoxide. Dimethyl sulfone and mixtures thereof are preferably cresol and Dimethylacetamide used.

To carry out the process according to the invention, the reaction components are kept at temperatures from 0 to 350 ° C. for a few minutes to several hours, with or without a solvent. The end of the reaction is indicated by the decrease in gas evolution and the increasing viscosity. It is sometimes advantageous to carry out the reaction in several stages. Thus, in a first step an adduct or condensate can be produced, which passes then at higher temperatures, possibly with chain extension or cross-linking, in the hochmolekula ^r e polyamideimide In some cases, it is recommended that the reaction under an inert gas such as nitrogen or argon to stir.

In general, it is advantageous to adjust the proportions to choose between the reaction components equivalent to the reactive groups, but there are also very substantial deviations possible from these stoichiometric ratios. The inventive reaction can through suitable catalysts are accelerated, e.g. B.

ίο by ßorfluorid and its adducts. Mineral acid. Carboxylic acids. Zinc chloride, tin (ll) chloride. Iron Π) chloride. Cobalt acetate, triethylenediamine. Phenyl - methyl - phospholine oxide, trialkyl - phosphine. Potassium acelal, zinc octoate. Dialkyl tin diacylate.

Titanium tetrabutylate and lead oxide. The lactams kalalysieien the reaction between isocyanates and carboxylic acids or anhydrides.

The polyamide-imides which can be prepared by the process according to the invention are distinguished by their special features Temperature resistance and are generally used as heat-resistant plastics, e.g. B. suitable as paints, foils and moldings. Their properties can vary for different areas of application by changing the stoichiometric ratios, the degree of condensation and by adding of fillers. Pigments and low and high molecular weight components, e.g. B. for the production of Wire enamels can be varied by mixing with polyesters.

- (O That in the following examples as a solvent The cresol used is a mixture of isomers, as it is produced industrially.

example 1

125 »4.4'-diisocyanato-diphenylmethane, 96 g of trimellitic anhydride and 57 g of caprolactam are slowly heated to 150 ° C. in 290 g of cresol. One remains in this temperature range until after about 2 hours the strong CO _: evolution has subsided.

and then the temperature is raised over a period of 1 to 2 hours to 2 (XI C. Subsequently nod:. 10 hours at this temperature a highly viscous solution is obtained of the condensate that still hot with 290 g Krcsol diluted au plates or glass plates first It is baked for 20 minutes at 200 ° C. and then for 20 minutes at 300 ° C. The IR spectrum contains the bands characteristic of imides and 1675 cm 'the bands characteristic of amides at 1725 and 1778 cm

Example 2

1 74 g of toluylene (2.4) diisocyanate, 113 g caprolactam and 192 g of trimellitic anhydride are stirred in 48Oi cresol at 190 to 200 ¹ C, until no more CO ₂ will escape mch.

To produce a wire enamel, the viscous *

Solution with 250 g of a polyester made of terephthalic acid, ethylene glycol and glycerin and 980 g of cresol mixed and baked at 200 and 300 "C to see light brown elastic paints.

Example 3

161 g of azo-4,4'-bis-phthalic anhydride, 84 g of Hcxa methylene diisocyanate and 98 g of ω-amino-dodecanoic acid-lactam are heated in 680 g of cresol to 190 ° C. for about 8 hours while stirring. One receives beir

⁴ I I 770 202

11 12

Baking at 190 ° and 250 ° C. gives a tough, clear solution in 460 g of dimethylacetamide for 6 hours at 80 ° C. and

Paint film. Stirred at 120 ° C. for 6 hours. You get a weak

. I ₄ viscous dark yellow solution, which at 200 and 300 C

be is pie I 4 _7U p _o] j _{en ho} i _ler tear resistance, elasticity and hardness

250 g 4,4'-diisocyanalodiphenylmethane, 192 g tri-5 are stoved,
mellitic anhydride and 226g caprolaclam in 670 g. -I ₁
Cresol are 4 hours at 140 ' ¹ C and then up to example 9
Completion of the condensation stirred at 200.degree. 136 g of an isocyanate with an isocyanate content of 30.9%. The end point is reached as soon as the solid components precipitated in the phosgenation of a condensation reaction are obtained again in solution of aniline and formaldehyde and no more gas evolution to 96 g of trimellitic anhydride and 56 g of caprolactam is observed. The solution is diluted with 700 g of cresol in 58O g of cresol with stirring for 12 hours and heated at 200 and 250 ° C. to form clear lacquer films at 180 ° C. Baked in at 200 and 300 ° C. gives a clear, hard lacquer film whose ο ■ . - - c 15 IR spectrum at 1715 and 1775 cm ~ 'those for imides ^hpi and at 1685 cm' those characteristic for amides

174 g toluylene (2,4) diisocyanate, 113 g caprolactam. Contains bands.

192 g of trimellitic anhydride and 960 g of cresol are unexpected technical advantages of the invention with stirring for 4 hours at 150 ^° C. and then heated to 200 ° C. until the process in accordance with the process of cessation of gas evolution. ₂₀ French patent specification 1,375,461 result from A clear solution is obtained which contains 31 g of glycol. the following comparison tests:
0.4 2 lead oxide and 0.8 g zinc octoate are added and an-, ",, .... _, .. _n ,,. .
is then held at 190 C for a further 2 hours. '· S ^{test eMASS the} inventive method, the baking at 200 ° C and 300 C yields clear, 56.6 g (0.5 mole) of caprolactam, 125 g (0.5 mol) of elastic films. 25 4,4'-diisocyanatodiphenylmethane and 96 g (0.5 mol). . Trimellitic anhydride are heated in 270 g of ^{cresol, for example b} 5 hours at 165 to 170C. The reaction

In 300 g of cresol, 56 g of caprolactam are first made with the evolution of carbon dioxide. Arrival and 12.4 g ethylene glycol and 125 g of 4,4'-diisopropyl closing is cyanatodiphenylmethan registered for 6 hours at 190 ⁰ C and. The reaction was then stirred at 210 ° C. for 5 hours. A mixture is obtained which is ^{subsequently stirred at 90 °} C. for 1 hour and a clear, viscous solution of the polyamideimide which is then mixed with 134 g of trimellitic anhydride. 0.2 g glass plate was added to a transparent, elastic lacquer lead oxide and 0.6 g zinc octoate. The mixture is heated is baked film whose mechanical Eigennurlangsam aufl50 ⁿ C, stirred for 4 hours at that transactions according to DIN 46453 were determined:
Temperature and leads the condensation through about 15 ". . . ... _no . , _{ηοο /}

1 hour of heating to 200 "C to end. The viscous elasticity. External fiber elongation 98%

The polyamide-iinide ester is dissolved at 200 and a heat snap zou e

300 C ^ baked into clear, tough lacquers and shows a softening temperature of 330 C

in the IR spectrum at 1720 and 1775cm " ¹ the door _T1 ,,, .." _r ..., "" .. · ,,. ",,,,

I mide, at 1673 cm - ^l the door amide and at 1736 cm ^&quot; ₄ o ^{IL Vcrsuch} S emaß French patent 1 375 461

the bands characteristic of esters. A solution of 100 g (0.4 mol) 4,4'-diisocyanato-

. I ₇ diphenylmethane in 279 g of cresol was on for 2 hours

Example / 100 to 110 ^c C heated. Then 76.8g

174 g of toluylene (2,4) diisocyanate, 113 g of caprolactam (0.4 mol) of trimellitic anhydride were added and that

and 192 g trimellitic anhydride in 480 g 45 mixture are 6 hours at 190 C and 20 hours

Kresoljeweilsbiszur evolution of gas heated 210 ^0C. A cloudy paint solution was thereby produced

heated to 150 and 2 (K) "C. It is now diluted with the result that only a heterogeneous one during stoving.

100 g of xylene and 450 g of cresol and is obtained when the layer becomes brittle.

Burn at! 90 and 300 "C hard dark brown lacquer - From these experiments it is clear that

movies. 50 surprisingly, the inventive poly

S Diel 8 amidimide is far better suited for painting than

'Products that can be obtained by implementing Polyiso

125 g of 4,4'-diisocyanatodiphenylmethane, 96 g of tricyanates with cyclic carboxylic acid anhydrides ge

Mellitic anhydride and 11.3 g of caprolactam are obtained according to French patent 1,375,461

Claims (1)

Patent claims: 1. Process for the preparation of high molecular weight Pplyamidimiden d-irch implementation of aliphatic, aromatic or aliphatic aromatic Diisocyanates with cyclic carboxylic acid anhydrides of the general formula